Phthalocyanine basic dyestuffs

ABSTRACT

A compound or a mixture of compounds of formula I    &lt;IMAGE&gt;  (I)  in which Pc is a phthalocyanine group (which may be metallized or metal-free); R1 is hydrogen or lower alkyl; Q and Q1 are both either -NR2R3 or are both -N(+)R4R5R6 An(-) where R2 to R6 are organic substituents. M is hydrogen or a cation; A is a lower alkylene or a lower alkenylene; An(-) is a non-chromophoric anion; m and n are average numbers from 0.3 to 4; p is an average number from 0 to 1; with the provisos that (i) m+n is an average number from 2 to 6; and (ii) Q and Q1 are not the same group.

This is a continuation of application Ser. No. 670,583, filed Nov. 13,1984, now abandoned, which in turn is a continuation-in-part of Ser. No.570,209, filed Jan. 12, 1984, now abandoned.

The invention relates to mixtures of phthalocyanine compounds containingat least two cationic groups or two basic groups.

According to the invention there is provided a compound or mixture ofcompounds of the formula (I) ##STR2## in which Pc is a metal-free ormetallised phthalocyanine group;

R₁ is hydrogen or unsubstituted C₁₋₄ alkyl;

Q and Q₁ are

either both of the formula --NR₂ R₃,

or are both of the formula --N.sup.⊕ R₄ R₅ R₆ An.sup.⊖

A is C₁₋₆ alkylene or C₂₋₆ alkenylene;

M is a cation or hydrogen;

An.sup.⊖ is a non-chromophoric anion;

m is an average number from 0.3 to 4 inclusive;

n is an average number from 0.3 to 4 inclusive;

p is an average number from 0 to 1 inclusive;

R₂ is hydrogen; unsubstituted C₁₋₁₂ alkyl; unsubstituted phenyl; C₁₋₄alkyl substituted by one phenyl group, the phenyl group beingunsubstituted or substituted by 1 to 3 unsubstituted C₁₋₄ alkyl groups;C₂₋₄ alkyl mono-substituted by OH other than in the α-position; or C₅₋₈cycloalkyl unsubstituted or substituted by 1 to 3 C₁₋₄ alkyl groups; and

R₃ is hydrogen, unsubstituted C₁₋₁₂ alkyl or C₂₋₄ alkyl substituted byOH; or

R₂ and R₃ together with the N-atom to which they are attached form a 5-or 6-membered heterocyclic saturated ring;

R₄ has a significance of R₂ other than hydrogen;

R₅ has a significance of R₃ other than hydrogen; or

R₄ and R₅ together with the N-atom to which they are attached form a 5-or 6-membered heterocyclic saturated ring; and

R₆ is unsubstituted C₁₋₁₂ alkyl, C₂₋₄ alkyl mono-substituted by --OHother other than in the α-position; or C₁₋₄ alkyl substituted byunsubstituted phenyl;

or R₄, R₅ and R₆ together with the N-atom to which they are attachedform a pyridinium ring unsubstituted or substituted by 1 or 2 C₁₋₄ alkylgroups;

with the provisos that

(i) m+n is an average number from 2 to 6 inclusive;

(ii) Q and Q₁ are not the same group.

In this specification where any symbol appears more than once in aformula unless indicated to the contrary its significances areindependent of one another.

Any alkyl, alkenylene, or alkylene group present is linear or branched.

Preferably when Q and Q₁ are --NR₂ R₃ and one group NR₂ R₃ is adialkylamino group then R₂ and R₃ of such dialkylamino group are thesame.

Preferably when Q and Q₁ are --NR₂ R₃ and both NR₂ R₃ groups aredialkylamino then each of R₂ and R₃ attached to the same nitrogen atomare the same.

Any alkyl, alkenylene or alkylene group present is preferably C₁₋₄.

Preferably when R₂ and R₃ or R₄ and R₅ together with the N-atom to whichthey are attached form a heterocyclic ring this is a morpholine,piperidine, pyrrolidine, piperazine unsubstituted or N-substituted by aC₁₋₄ alkyl group; each ring being C-unsubstituted or C-substituted by 1to 3 (preferably 1 to 2) C₁₋₄ alkyl groups.

Preferably in R₂ C₅₋₈ cycloalkyl is unsubstituted cyclopentyl orunsubstituted cyclohexyl.

Preferred compounds or mixtures of compounds of formula I are of formulaII ##STR3## in which Pc' is copper, cobalt, iron, zinc, aluminium ornickel phthalocyanine;

R₁ ' is hydrogen or methyl;

Q' and Q₁ ' are either both --NR₂ 'R₃ ' or are both --N.sup.⊕ R₄ 'R₅ 'R₆'An.sup.⊖

A' is C₁₋₄ alkylene or ##STR4## M' is hydrogen, sodium, lithium,potassium or ammonium m' is an average number from 0.3 to 3 inclusive;

n' is an average number from 0.3 to 3 inclusive;

p' is an average value of 0 to 0.7 inclusive;

R₂ ' is hydrogen, unsubstituted C₁₋₆ alkyl, β-hydroxyethyl,unsubstituted cyclohexyl, unsubstituted phenyl or unsubstituted benzyl;

R₃ ' is hydrogen, unsubstituted C₁₋₆ alkyl or β-hydroxyethyl; or R₂ 'and R₃ ' together with the N-atom to which they are attached form anunsubstituted morpholine, unsubstituted piperidine, unsubstitutedpyrrolidine, unsubstituted piperazine or ##STR5## R₄ ' has asignificance of R₂ ' except hydrogen; R₅ ' has a significance of R₃ 'except hydrogen or

R₄ ' and R₅ ' together with the N-atom to which they are attached form##STR6## R₆ ' is unsubstituted C₁₋₄ alkyl, β-hydroxyethyl or benzyl orR₄ ', R₅ ' and R₆ ' together with the N-atom to which they are attachedform an unsubstituted pyridinium or 2- or 3-methylpyridinium or 1,2- or1,3-dimethylpyridinium;

R₇ is an unsubstituted C₁₋₄ alkyl;

with the provisos that

(i) m'+n' is an average number from 2 to 4 inclusive;

(ii) Q' and Q₁ ' are not the same group.

More preferred compounds or mixtures of compounds of formula I are offormula III ##STR7## in which CuPc is copper phthalocyanine;

A" is --CH₂ --, --CH₂ CH₂ -- or ##STR8## Q" and Q₁ " are either both--NR₂ "R₃ " or are both --N.sup.⊕ R₄ "R₅ "R₆ "An.sup.⊖ ;

R₂ " is hydrogen, methyl, ethyl, n-propyl, isopropyl or butyl;

R₃ " (independently of R₂ ") has a significance of R₂ " or

R₂ " and R₃ " together with the N-atom to which they are attached forman unsubstituted morpholine, unsubstituted pyrrolidine, unsubstitutedpiperidine, unsubstituted piperazine ring; or N-methyl piperazine;

R₄ " is methyl or ethyl;

R₅ " is methyl or ethyl; or

R₄ " and R₅ " together with the N-atom to which they are attached form##STR9## R₆ " is methyl, ethyl or benzyl or R₄ ", R₅ " and R₆ " togetherwith the N-atom to which they are attached form an unsubstitutedpyridinium, 2- or 3-methylpyridinium or 1,2- or 1,3-dimethylpyridinium;

m" is an average number from 0.3 to 2.5 inclusive;

n" is an average number from 0.3 to 2.5 inclusive.

with the provisos that

(i) m"+n" is an average number from 2.1 to 3 inclusive; and

(ii) Q" and Q₁ " are not the same group; and

(iii) R₂ " and R₃ ", when alkyl, are the same.

In the above formulae I to III where appropriate:

Pc is preferably CuPc as defined above;

A is preferably A'; more preferably A"; most preferably A is --CH₂ --₁₋₂;

Q is preferably Q', more preferably Q";

Q₁ is preferably Q₁ ', more preferably Q₁ ";

M is preferably M';

m is preferably m'; more preferably m"; most preferably 1 to 1.5;

n is preferably n'; more preferably n"; most preferably 1 to 1.5;

p is preferably p';

R₁ is preferably R₁ ' more preferably is hydrogen.

R₂ is preferably R₂ ' more preferably R₂ ";

R₃ is preferably R₃ ' more preferably R₃ ";

R₄ is preferably R₄ ' more preferably R₄ ";

R₅ is preferably R₅ ' more preferably R₅ ";

R₆ is preferably R₆ ' more preferably R₆ ";

the cyclic significance of R₂ and R₃ are preferably those of R₂ ' and R₃' more preferably those of R₂ " and R₃ ";

the cyclic significances of R₄ and R₅ are preferably those of R₄ ' andR₅ ', more preferably those of R₄ " and R₅ ";

the cyclic significance of R₄, R₅ and R₆ are preferably those of R₄ ',R₅ ' and R₆ ', more preferably those of R₄ ", R₅ " and R₆ ".

Preferably when one of Q and Q₁ is a non-cyclic significance the otherof Q and Q₁ is a cyclic significance.

Preferably Q and Q₁ have at least a difference of two carbon atoms.

Compounds or mixtures of compounds of formula I can be prepared by

(i) reacting 1 mol of a compound of formula IV ##STR10## in which Hal ishalogen (preferably F, Cl or Br) and the other symbols are definedabove;

with m moles of a compound of formula V

    H--Q                                                       (V)

in water at a temperature of 20° to 50° C. (preferably 30° to 45° C.)and in a pH range of 9 to 12 (preferably 10 to 11) in the presence of abase followed by

(ii) reacting the resulting product with n moles of a compound offormula VI

    H--Q.sub.1 '                                               (VI)

in water at a temperature of 40° to 80° C. (preferably 50° to 60° C.)and at a pH of 9 to 12 (preferably 10 to 11) in the presence of a base.

Preferably in steps (i) and (ii) above the base is an alkali metalhydroxide for example KOH or NaOH.

Compounds of formula IV, V and VI are known or may be prepared fromknown compounds by known methods.

In the compounds or mixture of compounds of formula I the anionsAn.sup.⊖ can be any non-chromophoric anions such as those conventionalin basic dyestuff chemistry. Suitable anions include chloride, bromide,sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate,benzenesulfonate, oxalate, maleate, acetate, propionate, lactate,succinate, tartrate, malate, methanesulphonate and benzoate, as well ascomplex anions, for example, zinc chloride double salts and anions ofboric acid, citric acid, glycollic acid, diglycollic acid and adipicacid or addition products of orthoboric acid with polyalcohols with atleast one cis diol group present. These anions can be exchanged for eachother by ion exchange resins or by reaction with acids or salts, forexample via the hydroxide or bicarbonate or according to GermanOffenlegungsschrift No. 2,001,748 or No. 2,001,816.

The compounds or mixture of compounds of formula I are suitably workedup into solid or liquid preparations, for example by granulation or bydissolving in a suitable solvent. The compounds or mixture of compoundsof formula I may be used in quaternised form and/or in the form of asalt of a mineral or organic acid or in the form of an internal salt.The compounds or mixtures of compounds of formula I are suitable fordyeing, padding or printing on fibres, threads or textile materialsparticularly natural or regenerated cellulose materials for examplecotton, or synthetic polyamides or synthetic polyesters in which theanionic groups have been modified. Such a polyamide is described inBelgian Pat. No. 706,104 and such a synthetic polyester is described inU.S. Pat. No. 3,379,723.

The compounds or mixture of compounds of formula I may also be appliedto bast fibres such as hemp, flax, sisal, jute, coir or straw.

The textile material is dyed, printed or pad-dyed in accordance withknown methods. Acid modified-polyamide is dyed particularlyadvantageously in an aqueous, neutral or acid medium, at temperatures of60° C. to boiling point or at temperatures above 100° C. under pressure.

The textile material may also be dyed by the compounds or mixture ofcompounds of formula I in organic solvents, e.g. in accordance with thedirections given in German Offenlegunsschrift No. 2,437,549.

Cellulose material is mainly dyed by the exhaust process i.e. from along or short bath, at room temperature to boiling temperature,optionally under pressure, whereby the ratio of the bath is from 1:1 to1:100 and preferably from 1:20 to 1:50. If dyeing is effected from ashort bath, then the liquor ratio is 1:5 to 1:15. The pH of the dye bathvaries between 3 and 10 (for short and long dyebaths). Dyeing preferablytakes place in the presence of electrolytes.

Printing may be effected by impregnation with a printing paste producedby known methods.

The compounds or mixtures of compounds of formula I are also suitablefor dyeing or printing paper, e.g. for the production of bulk-dyed,sized and unsized paper. The dyestuffs may similarly be used for dyeingpaper by the dipping process. The dyeing of paper is effected by knownmethods.

The compounds or mixtures of compounds of formula I are also suitablefor dyeing or printing leather by known methods.

Dyeings with good fastness are obtained on both paper and leather.

Dyeings prepared with compounds or mixtures of compounds of formula I onpaper produce a substantially clear spent waste liquor which isimportant for environmental reasons. The dyes of formula I have goodbuild-up properties, do not run once applied to paper and are not pHsensitive. Dyeings produced with dyes of formula I have good lightfastness and the nuance on exposure for a long time to light fades tonein tone. The dyes of formula I have good wet-fastness properties notonly for water but also for milk, soap, water, sodium chloride solution,fruit juice, and sweetened mineral water. Further dyeings made with dyesof formula I are fast for alcoholic beverages due to a good alcoholfastness. Further, the dyes of formula I have good nuance stability.

The compounds or mixtures of compounds of formula I have good watersolubility. Furthermore, they exhibit very little to no bleeding.

In the following Examples all parts and percentages given are by weightand the temperatures given are in degrees Centigrade, unless indicatedto the contrary.

EXAMPLE 1

28 Parts (1/30 mol) of an average 50:50% mixture of bis- andtris(chloracetylamidomethyl)copper phthalocyanine is made into a pastewith 300 parts of water. The pH is brought to 7-8 by the addition of 30%NaOH solution.

2.84 Parts (1/30 mol) of piperidine is added whilst stirring at 20° to30°, after which the solution is warmed to 40° to 43°. The pH of thesolution is held at 10.5 to 11.0 by the dropwise addition of 4.5 parts(1/30 mol) of a 30% sodium hydroxide solution. The reaction isterminated as soon as the pH remains constant. The resulting dyestuffmixture is of the formula 1a ##STR11##

This mixture is fully dissolvable in 40 to 45% acetic acid solution.

10 Parts (1/10 mol) of dibutylamine is added to the reaction mixturecontaining the mixture of formula 1a and the mixture so formed isstirred at 55° to 60° until the pH reaches a constant value of 10.5 to11.0 by the dropwise addition of 6.7 parts (1/20 mol) of 30% solution ofsodium hydroxide.

The resulting dyestuff mixture is then filtered and is washed withsalt-free water and dried at 60° C.

The resulting dyestuff mixture is of the formula 1(b) ##STR12##

The mixture dissolves in dilute acetic acid solution and in dilutelactic acid and gives a brilliant blue colour. Paper dyed with thisdyestuff mixture has excellent wet fastness properties and the resultingdyebath is practically colourless. The dyeings so produced have goodlight fastness properties.

EXAMPLE 2

Instead of the mixture of bis- and tris-(chloracetylamidomethyl)copperphthalocyanine used in the method of Example 1, 26.6 parts of a mixtureof 90:10% bis- and tris-(chloracetylamidomethyl)copper phthalocyamine isused. The resulting dyestuff mixture is of formula 2a ##STR13##

The mixture has good solubility in dilute acetic acid solution andlactic acid solution and dyeings made with the mixture have goodfastness properties.

EXAMPLES 3 TO 10

Dyestuff mixtures of formula 3a ##STR14## in which Q, Q₁, m and n aredefined in the columns of the Table below can be prepared by a methodanalogous to that of Example 1 from known starting materials.

                                      TABLE                                       __________________________________________________________________________    EX. No.                                                                             Q          m   Q.sub.1          n                                       __________________________________________________________________________    3     N(C.sub.2 H.sub.5).sub.2                                                                 1   N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                   1.5                                     4     N(CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                      1   "                1.4                                            ##STR15## 1   "                1.4                                     6     "          1                                                                                  ##STR16##       1.4                                     7                                                                                    ##STR17##     N(CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                            1.4                                     8     "          1   N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                   1.3                                     9                                                                                    ##STR18## 1                                                                                  ##STR19##       1.3                                     10    "          0.3 "                2                                       __________________________________________________________________________

The dyestuff mixtures of Examples 3 to 10 dye paper a brilliant bluetone and the dyeings so produced have good fastness properties,particularly light fastness and wet fastness properties.

EXAMPLE 11

21 Parts (1/40 mol) of a 50% mixture of bis- andtris-chloracetylamidomethyl)copper phthalocyanine are stirred into 350parts of water and the mixture is brought to pH 7 to 8 by the additionof a 30% NaOH solution. 3.3 Parts (1/40 mol) of a 45% trimethylaminesolution are added and the reaction mixture is heated to 38° to 42°. ThepH of the solution is brought to 10 to 10.5 by the addition of 3.4 parts(1/40 mol) of a 30% NaOH solution. 6 Parts (3/40 mol) of pyridine areadded and the temperature is raised to 55° to 60° and by the addition ofabout 5.1 parts of a 30% NaOH solution the reaction mixture is held at apH of 10.5 to 11. After stirring for 3 hours the dyestuff is filteredand washed with neutral and salt-free water and dried. The resultingdyestuff mixture is of formula 11a ##STR20##

The dyestuff mixture of formula 11a dissolves in dilute acetic acid anddilute lactic acid solution and dyeings on paper made with the dyestuffmixture are blue and have good fastness properties in particular goodwet fastness properties.

Application Example A

70 Parts of chemically bleached sulphite cellulose obtained frompinewood and 30 parts of chemically bleached sulphite cellulose obtainedfrom birchwood are ground in 2000 parts of water in a Hollander. 0.2Parts of the dyestuff mixture of Example 1 are added into this pulp.Paper is produced from this pulp after mixing for 20 minutes. Theabsorbent paper which is obtained in this manner is dyed a blue tone andthe waste water is practically colourless.

Application Example B

0.5 Parts of the dyestuff mixture of Example 1 are dissolved in 100parts of hot water and cooled to room temperature. The solution is addedto 100 parts of chemically bleached sulphite cellulose which have beenground in a Hollander with 2000 parts of water. Sizing takes place aftera thorough mixing for 15 minutes. The paper which is produced from thismaterial has a blue tone of middle intensity and has good fastnessproperties.

Application Example C

An absorbent web of unsized paper is drawn at a temperature of 40° to50° C. through a dyestuff solution having the following composition:

0.5 parts of the dyestuff mixture of Example 1

0.5 parts of starch

99.0 parts of water.

The excess dyestuff solution is squeezed out through two rollers. Thedried web of paper is dyed a blue tone and has good fastness properties.

Application Example D

2 Parts of the dyestuff mixture of Example 1 are dissolved in 4000 partsof demineralised water at 40° C. 100 Parts of a prewetted cotton textilesubstrate are added and the bath is raised to boiling point over 30minutes and held at the boil for 1 hour, topping up with water wherenecessary. After removing the dyed web from the bath washing and drying,a blue dyeing is obtained with good light fastness and wet fastnessproperties. The dye exhausts practically totally and the waste water ispractically colourless.

Application Example E

100 Parts of freshly tanned and neutralized chrome leather are agitatedfor 30 minutes in a vessel with a dyebath of 250 parts of water and 1part of the dyestuff mixture of Example 1 at 55° C. and are then treatedin the same bath for 30 minutes with 2 parts of an anionic fatty liquorbased on sulphonated train oil. The leather is then dried and preparedin the normal way, giving a leather evenly dyed in a blue tone.

Other low affinity vegetable tanned leathers can be similarly dyed byknown methods.

Any one of the dyestuff mixtures of Examples 2 to 11 may be used inplace of that of Example 1 in any one of Application Examples A to E.

What is claimed is:
 1. A compound or mixture of compounds of the formula##STR21## in which Pc is a metal-free or metalized phthalocyaninegroup;A" is --CH₂ --, --CH₂ CH₂ -- or ##STR22## Q" and Q₁ " are both--NR₂ "R₃ "; M is a cation or hydrogen; R₁ ' is hydrogen or methyl; R₂ "is hydrogen, methyl, ethyl, n-propyl, isopropyl or butyl; R₃ ",independently of R₂ ", has a significance of R₂ " or R₂ " and R₃ "together with the N-atom to which they are attached form anunsubstituted morpholine, unsubstituted pyrrolidine, unsubstitutedpiperidine, unsubstituted piperazine or N-methyl piperazine; p' is anaverage number from 0 to 0.7, inclusive; m" is an average number from0.3 to 2.5, inclusive; and n" is an average number from 0.3 to 2.5,inclusive; with the provisos that(i) m"+n" is an average number from 2.1to 3, inclusive, and (ii) one of Q" and Q₁ " is non-cyclic and the otheris cyclic.
 2. A compound or mixture of compounds according to claim 1wherein M is M' where M' is hydrogen, lithium, sodium, potassium orammonium.
 3. A compound or mixture of compounds according to claim 2wherein Pc is Pc' where Pc' is copper, cobalt, iron, zinc, aluminum ornickel phthalocyanine.
 4. A compound or mixture of compounds accordingto claim 2, wherein, in any dialkylamino group as Q" or Q₁ ", R₂ " andR₃ " are the same.
 5. A compound or mixture of compounds according toclaim 3 wherein, in any dialkylamino group as Q" or Q₁ ", R₂ " and R₃ "are the same.
 6. A mixture of compounds according to claim 5 of theformula ##STR23## m" is an average number 1 and n" is an average number0.3 to 2.5 or n" is an average number 1 and m" is an average number 0.3to 2.5.
 7. A mixture according to claim 6 wherein m" is an averagenumber 1 and n" is an average number 0.3 to 2.5.
 8. A mixture accordingto claim 7 wherein n" is an average number 1.5.
 9. A mixture accordingto claim 7 wherein n" is an average number 1.3.